WO2011111831A1 - ピリジン環含有化合物、及びハロゲン化ピコリン誘導体及びテトラゾリルオキシム誘導体の製造方法 - Google Patents

ピリジン環含有化合物、及びハロゲン化ピコリン誘導体及びテトラゾリルオキシム誘導体の製造方法 Download PDF

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WO2011111831A1
WO2011111831A1 PCT/JP2011/055809 JP2011055809W WO2011111831A1 WO 2011111831 A1 WO2011111831 A1 WO 2011111831A1 JP 2011055809 W JP2011055809 W JP 2011055809W WO 2011111831 A1 WO2011111831 A1 WO 2011111831A1
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group
unsubstituted
substituted
formula
substituent
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PCT/JP2011/055809
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English (en)
French (fr)
Japanese (ja)
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秀和 宮崎
谷中　悟
坪倉　史朗
忠司 杉浦
野田　薫
顕吾 鈴木
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日本曹達株式会社
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Priority to US13/583,733 priority Critical patent/US8841458B2/en
Application filed by 日本曹達株式会社 filed Critical 日本曹達株式会社
Priority to JP2012504543A priority patent/JP5627038B2/ja
Priority to CN201180012762.8A priority patent/CN102791691B/zh
Priority to BR112012022823-4A priority patent/BR112012022823B1/pt
Priority to RU2012138410/04A priority patent/RU2512344C1/ru
Priority to BR122017023130-8A priority patent/BR122017023130B1/pt
Priority to KR1020127023288A priority patent/KR101409137B1/ko
Priority to BR122017023123-5A priority patent/BR122017023123B1/pt
Priority to AU2011225122A priority patent/AU2011225122B8/en
Priority to BR122017023128-6A priority patent/BR122017023128B1/pt
Priority to EP11753489.1A priority patent/EP2546236A4/de
Publication of WO2011111831A1 publication Critical patent/WO2011111831A1/ja
Priority to IL221847A priority patent/IL221847A/en
Priority to IL229968A priority patent/IL229968A/en
Priority to IL229967A priority patent/IL229967A/en
Priority to US14/173,338 priority patent/US8962848B2/en
Priority to US14/173,330 priority patent/US9012653B2/en
Priority to US14/173,352 priority patent/US9000178B2/en
Priority to US14/173,323 priority patent/US9018385B2/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the present invention provides (1) a pyridine ring-containing compound suitable as an agrochemical intermediate, and (2) a 2-substituted amino-6-halomethylpyridine derivative that is useful as a synthetic intermediate for agricultural chemicals and the like in high yield. And (3) a method for industrially advantageously producing a tetrazolyl oxime derivative having an excellent control effect against plant diseases.
  • the present application includes Japanese Patent Application No. 2010-056718 filed in Japan on March 12, 2010, Japanese Patent Application No. 2010-127207 filed in Japan on June 2, 2010, and Japan on May 19, 2010. Priority is claimed based on Japanese Patent Application No. 2010-115703 filed in Japan, the contents of which are incorporated herein by reference.
  • Patent Document 1 As a method for producing a halomethylpyridine derivative, for example, in Patent Document 1, a chlorinating agent such as oxalyl chloride is dropped into an acetonitrile solution of 2-chloro-5-acetaminomethylpyridine and dimethylformamide, and then the mixture is added. A process for producing 2-chloro-5-chloromethylpyridine by heating to 80 ° C. is described. Patent Document 2 discloses that aminomethylpyridine is reacted with a nitrosating agent or a diazotizing agent at a temperature of ⁇ 20 ° C. to + 50 ° C. in the presence of a diluent and optionally in the presence of hydrogen chloride. A method for producing chloromethylpyridines is described.
  • Patent Document 3 discloses 6-chloro-2- (chloromethyl) characterized by reducing 6-chloro-2- (trichloromethyl) pyridine or 6-chloro-2- (dichloromethyl) pyridine. A process for the preparation of pyridine is described.
  • tetrazolyl oxime derivatives described in Patent Document 4 and the like are excellent in bactericidal activity, and are considered promising as active ingredients of plant disease control agents.
  • a tetrazolylmethanone derivative represented by the formula (A) is reacted with hydroxylamine to obtain a tetrazolylhydroxyimino derivative represented by the formula (B), and then in the presence of a base, the formula (C
  • Patent Documents 1 to 3 disclose methods for producing halomethylpyridine derivatives.
  • Patent Documents 4 and 5 disclose a tetrazolyl oxime derivative having a structure similar to that of the compound of the present invention, which is proposed for use as a fungicide.
  • the present invention provides (1) a pyridine ring-containing compound suitable as an agricultural chemical intermediate, and (2) a 2-substituted amino-6-halomethylpyridine derivative useful as a synthetic intermediate for agricultural chemicals and the like in high yield. It is an object of the present invention to provide a process for producing a tetrazolyl oxime derivative excellent in control effect against plant diseases and industrially advantageously.
  • a pyridine ring-containing compound having a specific structure can be synthesized industrially advantageously and is useful as an intermediate for producing a tetrazolyloxime derivative exhibiting bactericidal activity
  • a 2-substituted amino-6-methylpyridine derivative By reacting a 2-substituted amino-6-methylpyridine derivative with a brominating agent in an organic solvent and then reacting the reaction product, a phosphite and a base in an organic solvent, a 2-substituted amino -6-bromomethylpyridine derivative can be produced in high yield, and (3) when a specific 2-substituted amino-6-halomethylpyridine derivative is reacted with a tetrazolylhydroxyimino derivative as a novel production intermediate A tetrazolyloxime derivative of the compound, a specific 2-substituted amino-6-halomethylpyridine derivative and a tetrazolylhydroxyimid Is reacted with a derivative, followed by the
  • a pyridine ring-containing compound represented by the formula (1) is as follows.
  • R 0 is a C1-6 alkoxy group, a C1-6 alkoxy C1-6 alkoxy group, a C1-6 alkoxy C1-6 alkyl group, or a 1,3-dioxane-2-yl C1-6 alkyl.
  • R 01 and R 02 each independently represents a C 1-6 alkyl group
  • R 1 represents a benzoyl group which may be substituted with a C1-2 alkoxycarbonyl group, an acetyl group or a nitro group
  • Z is a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, a formyl group, a carboxyl group, an unsubstituted or substituted amino group, an unsubstituted or substituted alkyl group, an unsubstituted or substituted group
  • R 1b represents an unsubstituted or substituted alkoxycarbonyl group
  • R 2b represents an unsubstituted or substituted alkoxycarbonyl group
  • an unsubstituted or substituted acyl group represents an unsubstituted or substituted aryloxycarbonyl group
  • an unsubstituted or substituted heterocyclic oxycarbonyl group represents an unsubstituted or substituted heterocyclic oxycarbonyl group.
  • Z is a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, a formyl group, a carboxyl group, an unsubstituted or substituted amino group, an unsubstituted or substituted alkyl group, an unsubstituted or substituted group An alkenyl group having a substituent, an unsubstituted or substituted alkynyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted heterocyclic group, OR 3 , S (O) p R 3 , Represents COR 3 or CO 2 R 3 (R 3 represents an unsubstituted or substituted amino group, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, unsubstituted Or an alkynyl group having a substituent, an aryl group having an unsubsubsti
  • [7] Represented by formula (6), comprising reacting a picoline bromide derivative represented by formula (4) and / or formula (5), a phosphite, and a base in an organic solvent.
  • a method for producing a picoline bromide derivative In the formula, R 1b represents an unsubstituted or substituted alkoxycarbonyl group, R 2b represents an unsubstituted or substituted alkoxycarbonyl group, an unsubstituted or substituted acyl group, an unsubstituted or substituted aryloxycarbonyl group, an unsubstituted or substituted heterocyclic oxycarbonyl group.
  • Z is a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, a formyl group, a carboxyl group, an unsubstituted or substituted amino group, an unsubstituted or substituted alkyl group, an unsubstituted or substituted group An alkenyl group having a substituent, an unsubstituted or substituted alkynyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted heterocyclic group, OR 3 , S (O) p R 3 , Represents COR 3 or CO 2 R 3 (R 3 represents an unsubstituted or substituted amino group, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, unsubstituted Or an alkynyl group having a substituent, an aryl group having an unsubsubsti
  • p represents the number of oxygen atoms in parentheses and is an integer of 0 to 2)
  • m represents the number of substitutions of Z and is an integer of 0 to 3.
  • m is 2 or more, a plurality of Z may be the same or different from each other.
  • R 1C represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group
  • R 2C represents an unsubstituted or substituted alkoxycarbonyl group, an unsubstituted or substituted acyl group
  • X represents a halogen atom
  • Z is a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, a formyl group, a carboxyl group, an unsubstituted or substituted amino group, an unsubstituted or substituted alkyl group, an unsubstituted or substituted group
  • Y represents an unsubstituted or substituted alkyl group
  • A is a halogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a cyano group, an unsubstituted or substituted alkylsulfonyl group, a nitro group, an unsubstituted or Represents an aryl group having a substituent
  • n c represents the number of substitutions of A and is an integer of 0 to 5, and when n c is 2 or more, A may be the same or different from each other.
  • R 1C represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group
  • R 2C represents an unsubstituted or substituted alkoxycarbonyl group, an unsubstituted or substituted acyl group
  • Z is a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, a formyl group, a carboxyl group, an unsubstituted or substituted amino group, an unsubstituted or substituted alkyl group, an unsubstituted or substituted group
  • p represents the number of oxygen atoms in parentheses and is an integer of 0 to 2)
  • m represents the number of substitutions of Z and is an integer of 0 to 3, and when m is 2 or more, the plurality of Zs may be the same or different from each other
  • Y represents an unsubstituted or substituted alkyl group
  • A is a halogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a cyano group, an unsubstituted or substituted alkylsulfonyl group, a nitro group, an unsubstituted or Represents an aryl group having a substituent
  • n c represents the number of substitutions of A and is an integer of 0 to 5, and when n c is 2 or more, A may be the same or different from each other.
  • R 1C represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group
  • R 2C represents an unsubstituted or substituted alkoxycarbonyl group, an unsubstituted or substituted acyl group
  • X represents a halogen atom
  • Z is a halogen atom, cyano group, nitro group, hydroxyl group, thiol group, formyl group, carboxyl group, unsubstituted or substituted amino group, unsubstituted or substituted alkyl group, unsubstituted or substituted group
  • OR 3 S (O) p R 3 , Represents COR 3 or CO 2 R 3 (R 3 represents an unsubstit
  • p represents the number of oxygen atoms in parentheses and is an integer of 0 to 2)
  • m represents the number of substitutions of Z and is an integer of 0 to 3, and when m is 2 or more, the plurality of Zs may be the same or different from each other
  • Y represents an unsubstituted or substituted alkyl group
  • A is a halogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a cyano group, an unsubstituted or substituted alkylsulfonyl group, a nitro group, an unsubstituted or Represents an aryl group having a substituent
  • n c represents the number of substitutions and is an integer of 0 to 5, and when n c is 2 or more, As may be the same or different from each other.
  • the pyridine ring-containing compound according to the present invention is useful as an intermediate for producing a tetrazolyl oxime derivative that can be synthesized industrially advantageously and exhibits bactericidal activity. Further, according to the production method of the present invention, a 2-substituted amino-6-halomethylpyridine derivative can be obtained with high selectivity and high yield, and a tetrazolyloxime derivative excellent in controlling effect against plant diseases can be obtained. It can be produced industrially advantageously.
  • Pyridine ring-containing compound suitable as an agrochemical intermediate is a compound represented by the formula (1).
  • the compound can be synthesized as follows.
  • a compound represented by the formula (12) according to the present invention (hereinafter referred to as “compound (12)”) is a compound represented by the formula (11) (hereinafter referred to as “compound (11)”).
  • R 1 -L can be obtained by acting.
  • L represents a leaving group such as a halogen atom.
  • Examples of the compound represented by R 1 -L include methoxycarbonyl chloride, ethoxycarbonyl chloride, acetyl chloride, benzoyl chloride, p-nitrobenzoyl chloride and the like.
  • the compound represented by the formula (13) according to the present invention (hereinafter referred to as “compound (13)”) is obtained by halogenating the compound (12).
  • the halogenation reaction can be performed by a known method. In the halogenation reaction, halogen alone, sulfuryl chloride, phosphorus pentachloride, N-chlorosuccinimide, N-bromosuccinimide, 1,3-dibromo-5,5-dimethylhydantoin, anhydrous copper chloride, aluminum chloride, etc. Can be used.
  • R 0 represents a C1-6 alkoxy group, a C1-6 alkoxy C1-6 alkoxy group, a C1-6 alkoxy C1-6 alkyl group, 1,3-dioxane-2-yl C1- A 6 alkyl group, a CR 01 C ( ⁇ NOR 02 ) group (R 01 and R 02 each independently represents a C 1-6 alkyl group);
  • Examples of the C1-6 alkoxy group for R 0 include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, n -Pentyloxy group, n-hexyloxy group and the like.
  • Examples of the C1-6 alkoxy group of R 0 include a methoxymethoxy group, an ethoxymethoxy group, a methoxyethoxy group, a 3-ethoxypropoxy group, a 2-ethoxybutoxy group, a 4-butoxybutoxy group, and a 1-butoxy group.
  • Examples include a pentoxy group, a 3-isopropoxy-2-methylpropoxy group, and 1-methoxy-2-ethoxyethoxy.
  • Examples of the C 1-6 alkoxy C 1-6 alkyl group represented by R 0 include a methoxymethyl group, an ethoxymethyl group, a methoxyethyl group, a methoxypropyl group, an ethoxybutyl group, a methoxybutyl group, a methoxyhexyl group, a propoxyoctyl group, 2 Examples include -methoxy-1,1-dimethylethyl group, 1-ethoxy-1-methylethyl group, 1-ethoxy-2-methoxyethyl group, and the like.
  • Examples of the 1,3-dioxane-2-yl C1-6 alkyl group of R 0 include a 1,3-dioxane-2-yl-methyl group, a 1,3-dioxane-2-yl-ethyl group, and the like. It is done.
  • R 01 and R 02 of the CR 01 C ( ⁇ NOR 02 ) group of R 0 are each independently a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, n-hexyl, etc. Represents a C1-6 alkyl group.
  • R 1 represents a benzoyl group which may be substituted with a C1-2 alkoxycarbonyl group, an acetyl group or a nitro group.
  • Examples of the C1-2 alkoxycarbonyl group for R 1 include a methoxycarbonyl group and an ethoxycarbonyl group.
  • Examples of the benzoyl group optionally substituted by the nitro group of R 1 include a p-nitrobenzoyl group.
  • Z and m in Formula (1), Formula (12), and Formula (13) represent Z and m similar to Z and m in Formula (7) described below.
  • X in Formula (1) represents a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a chlorine atom or a bromine atom is preferable, and a bromine atom is particularly preferable.
  • the compound (1) according to the present invention is useful as an intermediate for producing a tetrazolyl oxime derivative exhibiting bactericidal activity.
  • the production method of a halogenated picoline derivative according to the present invention is represented by the formula (2): A step B1 of reacting the represented compound with a halogenating agent in an organic solvent, and a step B2 of reducing the reaction product obtained in the step B1.
  • the raw material used in the production method of the present invention is a compound represented by the formula (2).
  • R 1b in formula (2) represents an unsubstituted or substituted alkoxycarbonyl group.
  • the substituent is not particularly limited as long as it is inert in the halogenation reaction.
  • the alkoxy group in the alkoxycarbonyl group is preferably composed of 1 to 6 carbon atoms.
  • a methoxycarbonyl group, an ethoxycarbonyl group, an i-propoxycarbonyl group, an n-propoxycarbonyl group, an n-butoxycarbonyl group, an i-butoxycarbonyl group, an s-butoxycarbonyl group examples thereof include a t-butoxycarbonyl group.
  • alkoxycarbonyl group having a substituent in R 1b examples include a cyanomethoxycarbonyl group, 1-cyanoethoxycarbonyl group, 2-cyanoethoxycarbonyl group, nitromethoxycarbonyl group, chloromethoxycarbonyl group, fluoromethoxycarbonyl group, difluoromethoxycarbonyl Group, trifluoromethoxycarbonyl group, 2-fluoroethoxycarbonyl group, 2,2,2-trifluoroethoxycarbonyl group, methoxymethoxycarbonyl group, ethoxymethoxycarbonyl group, 1-methoxyethoxycarbonyl group, 2-methoxyethoxycarbonyl group And 2-chloroethoxymethoxycarbonyl group.
  • R 1b is preferably an unsubstituted alkoxycarbonyl group, more preferably an unsubstituted alkoxycarbonyl group having 1 to 6 carbon atoms constituting the alkoxy group, and particularly preferably a t-butoxycarbonyl group.
  • R 2b in formula (2) is an unsubstituted or substituted alkoxycarbonyl group, an unsubstituted or substituted acyl group, an unsubstituted or substituted aryloxycarbonyl group, or an unsubstituted group Or the heterocyclic oxycarbonyl group which has a substituent is shown.
  • Examples of the unsubstituted alkoxycarbonyl group for R 2b include a methoxycarbonyl group, an ethoxycarbonyl group, an i-propoxycarbonyl group, an n-propoxycarbonyl group, an n-butoxycarbonyl group, an i-butoxycarbonyl group, an s-butoxycarbonyl group, Examples thereof include a t-butoxycarbonyl group.
  • alkoxycarbonyl group having a substituent in R 2b examples include a cyanomethoxycarbonyl group, 1-cyanoethoxycarbonyl group, 2-cyanoethoxycarbonyl group, nitromethoxycarbonyl group, chloromethoxycarbonyl group, fluoromethoxycarbonyl group, difluoromethoxycarbonyl Group, trifluoromethoxycarbonyl group, 2-fluoroethoxycarbonyl group, 2,2,2-trifluoroethoxycarbonyl group, methoxymethoxycarbonyl group, ethoxymethoxycarbonyl group, 1-methoxyethoxycarbonyl group, 2-methoxyethoxycarbonyl group And 2-chloroethoxymethoxycarbonyl group.
  • the acyl group in R 2b is a group in which a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group is bonded to a carbonyl group.
  • the unsubstituted acyl group include formyl group, acetyl group, propionyl group, n-propylcarbonyl group, n-butylcarbonyl group, octanoyl group, i-propylcarbonyl group, i-butylcarbonyl group, pivaloyl group, isovaleryl group, etc.
  • alkenylcarbonyl group such as an acryloyl group and a methacryloyl group
  • an alkynylcarbonyl group such as a propioyl group
  • an arylcarbonyl group such as a benzoyl group
  • a heterocyclic carbonyl group such as a 2-pyridylcarbonyl group and a thienylcarbonyl group
  • Examples of the acyl group having a substituent in R 2b include a fluoroacetyl group, a chloroacetyl group, a nitroacetyl group, a cyanoacetyl group, a methoxyacetyl group, a dibromoacetyl group, a trifluoroacetyl group, a trichloroacetyl group, a tribromoacetyl group, Examples include 3,3,3-trifluoropropionyl group, 3,3,3-trichloropropionyl group, 2,2,3,3,3-pentafluoropropionyl group, 4-chlorobenzoyl group and the like.
  • aryloxycarbonyl group for R 2b a phenyloxycarbonyl group, a 1-naphthyloxycarbonyl group, a 2-naphthyloxycarbonyl group, an azulenyloxycarbonyl group, an indenyloxycarbonyl group, an indanyloxycarbonyl group, Examples include a tetralinyloxycarbonyl group.
  • Examples of the aryloxycarbonyl group having a substituent in R 2b include 6-methylphenyloxycarbonyl group, 4-methylphenyloxycarbonyl group, 4-fluorophenyloxycarbonyl group, 4-chlorophenyloxycarbonyl group, 2,4-dichlorophenyl.
  • Oxycarbonyl group 3,4-dichlorophenyloxycarbonyl group, 3,5-dichlorophenyloxycarbonyl group, 2,6-difluorophenyloxycarbonyl group, 4-trifluoromethylphenyloxycarbonyl group, 4-methoxyphenyloxycarbonyl group, 3,4-dimethoxyphenyloxycarbonyl group, 3,4-methylenedioxyphenyloxycarbonyl group, 3-phenoxyphenyloxycarbonyl group, 4-trifluoromethoxyphenyloxycal Group, 4-methoxy-1-naphthyloxycarbonyl group, and the like.
  • Examples of the unsubstituted heterocyclic oxycarbonyl group in R 2b include a furan-2-yloxycarbonyl group, a furan-3-yloxycarbonyl group, a thiophen-2-yloxycarbonyl group, a thiophen-3-yloxycarbonyl group, Pyrrol-2-yloxycarbonyl group, pyrrol-3-yloxycarbonyl group, oxazol-2-yloxycarbonyl group, oxazol-4-yloxycarbonyl group, oxazol-5-yloxycarbonyl group, thiazol-2-yl Oxycarbonyl group, thiazol-4-yloxycarbonyl group, thiazol-5-yloxycarbonyl group, isoxazol-3-yloxycarbonyl group, isoxazol-4-yloxycarbonyl group, isoxazol-5-yloxycarbonyl Group, Sothiazol-3-yloxycarbonyl
  • heterocyclic oxycarbonyl group having a substituent in R 2b examples include 3-trifluoromethylpyridin-2-yloxycarbonyl group, 4-trifluoromethoxy-2-pyridyloxycarbonyl group, 3-methyl-1-pyrazolyloxycarbonyl Group, 4-trifluoromethyl-1-imidazolyloxycarbonyl group, 3,4-difluoropyrrolidinooxycarbonyl group and the like.
  • R 2b in formula (2) is preferably an unsubstituted or substituted benzoyl group.
  • the substituent that the benzoyl group has is not particularly limited as long as it is inactive in the halogenation reaction.
  • Examples of the benzoyl group having a substituent in R 2b include a 2,6-dimethoxybenzoyl group, a 3,5-nitrobenzoyl group, a 2,4,6-trichlorobenzoyl group, and a 4-chlorobenzoyl group.
  • Z and m in Formula (2) represent Z and m similar to Z and m in Formula (7) described below.
  • the halogenating agent used in step B1 is not particularly limited as long as it is used for halogenation in a known synthesis reaction.
  • the halogenating agent includes a compound that itself becomes a halogenating agent and a compound that can be converted into a halogenating agent in the reaction system.
  • halogenating agents include bromine (Br 2 ), chlorine (Cl 2 ), hydrogen bromide, hydrogen chloride, lithium bromide, potassium bromide, sodium bromide, magnesium bromide, calcium bromide, barium bromide
  • Metal bromides such as aluminum bromide, phosphorus tribromide, phosphorus pentabromide; ammonium bromide salts such as ammonium bromide, tetramethylammonium bromide, tetraethylammonium bromide, tetra-n-butylammonium bromide; trimethylsilyl bromine BrF, BrF 3 , BrF 5 , BrCl, BrCl 3 , bromine / pyridine complex, 1,3-dibromo-5,5-dimethylhydantoin, 1,3-diiodo-5,5-dimethylhydantoin, thionyl bromide, Chlorite, hypobromite, cyanuri
  • the amount of the halogenating agent to be used is not particularly limited, but is preferably 0.1 to 10 mol, more preferably 1 to 5 mol as a halogen atom with respect to 1 mol of the compound represented by the formula (2). .
  • Examples of the organic solvent used in Step B1 include ethers such as diethyl ether, butyl methyl ether, tetrahydrofuran, dioxane, dimethoxyethane; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, dichloroethylene.
  • ethers such as diethyl ether, butyl methyl ether, tetrahydrofuran, dioxane, dimethoxyethane
  • chlorobenzene dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, dichloroethylene.
  • Halogenated hydrocarbons aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane; such as methyl acetate, ethyl acetate and propyl acetate Esters; acetone, methyl ethyl ketone, cyclohexanone, acetonitrile, propionitrile, N, N-dimethylformamide, dimethyl sulfoxide, hexamethylphosphoric acid Amide, sulfolane, dimethylacetamide, polar aprotic solvents such as N- methyl pyrrolidone; protic solvent such as acetic acid; and water.
  • aromatic hydrocarbons such as benzene, toluene and xylene
  • aliphatic hydrocarbons such as pentane, hexane, hept
  • step B1 it is preferable to perform step B1 in the presence of a base.
  • a base When the base is present in the reaction system, side reactions are suppressed, and the halogenation reaction to the methyl group in the compound represented by the formula (2) becomes easier to proceed selectively.
  • Bases include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide; sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, hydrogen carbonate Carbonates such as sodium and potassium bicarbonate; hydrides such as sodium hydride and calcium hydride; metal alkoxides such as sodium methoxide, sodium ethoxide and magnesium methoxide; triethylamine, diisopropylethylamine, pyridine, N, N-dimethyl Aminopyridine, 1,4-diazabicyclo [2.2.2] octane, 4- (dimethylamino) pyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4 .3.0] Organic such as non-5-ene Group; and the like. These bases can be used alone or in combination of two or more. Of these, sodium bicarbonate is preferred
  • the reaction between the compound represented by the formula (2) and the halogenating agent is not particularly limited in the procedure.
  • the reaction may be carried out by adding a compound represented by the formula (2) and, if necessary, sodium bicarbonate to an organic solvent, and gradually adding a halogenating agent thereto.
  • the temperature from the start of the reaction to the end of the reaction may be constant or may be changed, but is preferably in the range of 0 to 200 ° C, more preferably in the range of room temperature to 150 ° C.
  • step B1 the methyl group in the compound represented by the formula (2) is selectively halogenated.
  • a monohalogenated picoline derivative represented by the formula (3), a dihalogenated picoline derivative represented by the formula (14) and / or a trihalogenated picoline derivative represented by the formula (15) Is obtained.
  • the present invention performs step B2 described below.
  • the technique for reducing the mixed reaction product of formula (3), formula (14), and formula (15) obtained in step B1 is not particularly limited.
  • a method comprising reacting the reaction product obtained in step B1 in an organic solvent in the presence of an acid and a metal; reaction obtained in step B1 by adding hydrogen in an organic solvent And a method including reacting the product.
  • the acid used in the above method include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as acetic acid, propionic acid and butyric acid.
  • the metal used in the above method include zinc, iron, tin, cobalt, nickel, and aluminum. The metal is preferably a fine powder.
  • the amount of each acid and metal used is not particularly limited as long as it is an amount sufficient to generate the amount of hydrogen necessary for the reduction.
  • the amount of hydrogen required is preferably 0.6 to 1.5 moles with respect to 1 mole of the halogenated picoline derivative represented by the formula (14), and the halogenated picoline derivative 1 represented by the formula (15)
  • the amount is preferably 1.2 to 3.0 mol with respect to mol.
  • the reduction reaction can usually be performed at a temperature ranging from ⁇ 20 ° C. to the reflux temperature, preferably 20 to 40 ° C.
  • step B1 and X When the reaction product obtained by using a brominating agent as the halogenating agent in step B1 and X is a bromine atom is reduced, the reaction product obtained in step B1, ie, the formula (4) And a method comprising reacting a picobromide derivative represented by formula (5) and / or a bromide picoline derivative represented by formula (5), a phosphite, and a base in an organic solvent as a preferred method. Can be mentioned.
  • the phosphite used in the above method is represented by P (OR) 3 and has a phosphorus oxidation number of +3.
  • R is a hydrogen atom, an alkyl group, an aryl group or the like, and at least one of the three Rs is a group other than a hydrogen atom.
  • Phosphites include triphenyl phosphite, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, trinonyl phosphite, tridecyl phosphite, trioctyl phosphite, tri Octadecyl phosphite, distearyl pentaerythritol diphosphite, tricyclohexyl phosphite, monobutyl diphenyl phosphite, monooctyl diphenyl phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butyl Phenyl) pentaerythritol phosphite, bis (2.6-di-tert-butyl-4-methylphenyl) pentaerythri
  • the amount of phosphite used is preferably 0.1 to 20 mol per mol of the picoline bromide derivative represented by the formula (4).
  • the picoline bromide derivative 1 represented by the formula (5) Preferably it is 0.2-40 mol with respect to mol.
  • Examples of the base used in the above method include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide; sodium carbonate, potassium carbonate and magnesium carbonate. Carbonates such as calcium carbonate; hydrides such as sodium hydride and calcium hydride; metal alkoxides such as sodium methoxide, sodium ethoxide and magnesium methoxide; triethylamine, diisopropylethylamine, pyridine, N, N-dimethylaminopyridine 1,4-diazabicyclo [2.2.2] octane, 4- (dimethylamino) pyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3 .0] organic bases such as non-5-ene; It is below.
  • alkali metal hydroxides such as sodium hydroxide and potassium hydroxide
  • the amount of the base used is preferably 0.1 to 10 moles per mole of picoline bromide derivative represented by formula (4), and is 1 mole per mole of picoline bromide derivative represented by formula (5).
  • the amount is preferably 0.2 to 20 mol.
  • the reaction of the reaction product obtained in Step B1, the phosphite, and the base is not particularly limited in the procedure.
  • the reaction may be performed while gradually adding a phosphite ester, a base, and, if necessary, a phase transfer catalyst to the organic solvent solution containing the reaction product obtained in step B1.
  • the temperature from the start of the reaction to the end of the reaction may be constant or may vary, but is preferably in the range of ⁇ 70 ° C. to + 100 ° C., more preferably in the range of ⁇ 10 ° C. to + 50 ° C. It is.
  • the organic solvent used in the step B2 is not particularly limited, and examples thereof include the same organic solvents used in the step B1.
  • the reaction solution obtained in step B1 can be used as it is in step B2 without recovering the reaction product from the reaction solution obtained in step B1.
  • phase transfer catalyst examples include quaternary ammonium salts; quaternary phosphonium salts such as tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, benzyltrimethylphosphonium chloride, benzyltrimethylphosphonium bromide; 12-crown-4,18-crown-6 And macrocyclic polyethers such as benzo-18-crown-6, and the like. Of these, quaternary ammonium salts are preferred.
  • Quaternary ammonium salts include chlorides such as tetramethylammonium chloride, tetraethylammonium chloride, tetra-n-propylammonium chloride, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyltripropylammonium chloride; tetramethylammonium bromide, tetraethylammonium chloride Bromides, tetra-n-propylammonium bromide, tetrabutylammonium bromide, benzyltrimethylammonium bromide, benzyltriethylammonium bromide, benzyltripropylammonium bromide, etc.
  • chlorides such as tetramethylammonium chloride, tetraethylammonium chloride, tetra-n-propylammonium chloride, benzyltri
  • phase transfer catalyst used is preferably 0.001 mol to 10 mol, more preferably 0.01 to 1 mol, relative to 1 mol of the compound represented by the formula (2).
  • the dihalogenated picoline derivative represented by the formula (14) and / or the trihalogenated picoline derivative represented by the formula (15) is converted into a monohalogenated picoline represented by the formula (3). Converted to a derivative. This increases the content of the monohalogenated picoline derivative represented by the formula (3) in the reaction system and facilitates isolation.
  • the halogenated picoline derivative obtained by the production method of the present invention is used as an intermediate for producing an active ingredient of an agrochemical formulation that assists the growth of agricultural and horticultural crops, and as an intermediate for producing an active ingredient of an adhesion inhibitor for shellfish and shellfish. It is useful as an intermediate for producing an active ingredient of an agent, or as an intermediate for producing an active ingredient of an antibacterial / antifungal agent for walls, bathtubs, shoes and clothes. By passing through this production intermediate, active ingredients such as agrochemical preparations, bactericides, antibacterial / antifungal agents and the like can be produced inexpensively and efficiently.
  • the tetrazolyl oxime derivative represented by the formula (9) is a novel substance, and is represented by the formula (10 It is useful as an intermediate for producing a tetrazolyl oxime derivative represented by:
  • the method for producing a tetrazolyl oxime derivative represented by the formula (9) comprises a step of reacting a halogenated picoline derivative represented by the formula (7) with a tetrazolyl hydroxyimino derivative represented by the formula (8). C1 is included.
  • the method for producing a tetrazolyloxime derivative represented by the formula (10) includes the step C1 and the step C2 in which a base is allowed to act on the reaction product in the step C1.
  • the raw material of the production method according to the present invention is a halogenated picoline derivative represented by the formula (7).
  • R 1C in formula (7) represents an unsubstituted or substituted alkyl group, or an unsubstituted or substituted alkoxy group.
  • the substituent in R 1C is not particularly limited as long as it is inert to the reaction with the tetrazolylhydroxyimino derivative represented by the formula (8).
  • the alkyl group in R 1C may be linear, branched, or cyclic.
  • the alkyl group preferably has 1 to 6 carbon atoms.
  • Examples of the unsubstituted alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, n -Octyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, 2,2-dimethylcyclopropyl group, menthyl group and the like.
  • alkyl group having a substituent chloromethyl group, fluoromethyl group, trifluoromethyl group, methoxymethyl group, ethoxymethyl group, methoxyethyl group, methoxypropyl group, ethoxybutyl group, methoxybutyl group, methoxyhexyl group, Propoxyoctyl group, 2-methoxy-1,1-dimethylethyl group, 1-ethoxy-1-methylethyl group, carbomethoxymethyl group, 1-carboethoxy-2,2-dimethyl-3-cyclopropyl group; hydroxymethyl Group, hydroxyethyl group, 1-hydroxypropyl group; and the like.
  • a haloalkyl group is preferred.
  • the alkoxy group for R 1C may be linear, branched, or cyclic.
  • the alkoxy group preferably has 1 to 6 carbon atoms.
  • Examples of the unsubstituted alkoxy group include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, n-pentyloxy group, n-hexyloxy group, n-decyloxy group; cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, menthyloxy group and the like.
  • alkoxy group having a substituent examples include a chloromethoxy group, a fluoromethoxy group, a trifluoromethoxy group, a methoxymethoxy group, an ethoxymethoxy group, a methoxyethoxy group, a 3-ethoxypropoxy group, a 2-ethoxybutoxy group, 4- Examples include butoxybutoxy group, 1-butoxypentoxy group, fluoromethoxymethoxy group, dichloromethoxymethoxy group, 1,2-dibromo-3-methoxypropoxy group, 3-isopropoxy-2-methylpropoxy group and the like.
  • R 2C represents an unsubstituted or substituted alkoxycarbonyl group or an unsubstituted or substituted acyl group, and specific examples thereof include those similar to the above R 2b .
  • R 2C in formula (7) is preferably an unsubstituted or substituted benzoyl group.
  • benzoyl group having a substituent include a 2,6-dimethoxybenzoyl group, a 3,5-nitrobenzoyl group, a 2,4,6-trichlorobenzoyl group, and a 4-chlorobenzoyl group.
  • X in the formula (7) represents a halogen atom.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a chlorine atom or a bromine atom is preferable.
  • Z in the formula (7) is a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, a formyl group, a carboxyl group, an unsubstituted or substituted amino group, an unsubstituted or substituted alkyl group, An unsubstituted or substituted alkenyl group, an unsubstituted or substituted alkynyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted heterocyclic group, OR 3 , S ( O) shows the p R 3, COR 3 or CO 2 R 3,.
  • the halogen atom in Z can be the same as the halogen atom in X.
  • the unsubstituted amino group in Z is a group having the structure NH 2- .
  • the amino group having a substituent include a methylamino group, a dimethylamino group, a methylethylamino group, a diethylamino group, a t-butoxycarbonylmethylamino group, a t-butoxycarbonylamino group, an acetylmethylamino group, an acetylethylamino group, A benzoylmethylamino group etc. are mentioned.
  • Examples of the unsubstituted or substituted alkyl group for Z include the same as the unsubstituted or substituted alkyl group for R 1C .
  • the unsubstituted or substituted alkenyl group for Z preferably has 2 to 8 carbon atoms.
  • Examples of the unsubstituted alkenyl group include vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-2-propenyl group, 2-methyl-2 -Propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-methyl-2-butenyl group, 2-methyl-2-butenyl group, 1-hexenyl group, 2-hexenyl group Group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group and the like.
  • alkenyl group having a substituent examples include 2-chloroethenyl group, 2-fluoroethenyl group, 3,3,3-trifluoro-1-pentenyl group, 1,2,2-trifluoroethenyl group, 2,3,3 Examples include 3-trifluoro-2-propenyl group, 2,3,3-triiodo-2-propenyl group, 2-methoxyethenyl group and the like.
  • the unsubstituted or substituted alkynyl group for Z preferably has 2 to 8 carbon atoms.
  • unsubstituted alkynyl groups include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-methyl-2-propynyl group, 2-methyl-3 -Butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 2-methyl-3-pentynyl, 1-hexynyl, 1,1 -Dimethyl-2-butynyl group and the like.
  • alkynyl group having a substituent examples include 2-chloroethynyl group, 2-fluoroethynyl group, 3-fluoro-1-propynyl group, 3,3,3-trifluoro-1-propynyl group, 3-fluoro-2- Examples include propynyl group and 3-iodo-2-propynyl group.
  • the unsubstituted or substituted aryl group in Z is a monocyclic or polycyclic aryl group.
  • the polycyclic aryl group as long as at least one ring is an aromatic ring, the remaining ring may be a saturated alicyclic ring, an unsaturated alicyclic ring, or an aromatic ring.
  • the unsubstituted aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an azulenyl group, an indenyl group, an indanyl group, and a tetralinyl group.
  • Examples of the aryl group having a substituent include 6-methylphenyl group, 4-methylphenyl group, 4-fluorophenyl group, 4-chlorophenyl group, 2,4-dichlorophenyl group, 3,4-dichlorophenyl group, 3,5- Dichlorophenyl group, 2,6-difluorophenyl group, 4-trifluoromethylphenyl group, 4-methoxyphenyl group, 3,4-dimethoxyphenyl group, 3,4-methylenedioxyphenyl group, 3-phenoxyphenyl group, 4 -Trifluoromethoxyphenyl group, 4-methoxy-1-naphthyl group and the like can be mentioned.
  • the unsubstituted heterocyclic group in Z includes furan-2-yl group, furan-3-yl group, thiophen-2-yl group, thiophen-3-yl group, pyrrol-2-yl group, and pyrrol-3- Yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isoxazol-3- Yl group, isoxazol-4-yl group, isoxazol-5-yl group, isothiazol-3-yl group, isothiazol-4-yl group, isothiazol-5-yl group, imidazol-2-yl group, Imidazol-4-yl group, imidazol-5-yl group, pyrazol-3-yl group, pyrazol-4-yl group, pyrazol-5-yl group, 1,
  • heterocyclic group having a substituent examples include 3-trifluoromethylpyridin-2-yl group, 4-trifluoromethoxy-2-pyridyl group, 3-methyl-1-pyrazolyl group, 4-trifluoromethyl-1- Examples include imidazolyl group and 3,4-difluoropyrrolidino group.
  • OR 3 S (O ) p R 3, COR 3 and CO 2 R 3 in R 3 is an amino group having unsubstituted or substituted group, an alkyl group having an unsubstituted or substituted, unsubstituted A substituted or substituted alkenyl group, an unsubstituted or substituted alkynyl group, an unsubstituted or substituted aryl group, or an unsubstituted or substituted heterocyclic group.
  • p represents the number of oxygen atoms in parentheses and is an integer from 0 to 2.
  • R 3 an unsubstituted or substituted amino group, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted alkynyl group, unsubstituted
  • the aryl group having or a substituent and the heterocyclic group having no substituent or a substituent the same groups as those described in the description of R 1C and Z can be mentioned.
  • OR 3 include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, s-butoxy group, i-butoxy group, t-butoxy group, methoxymethoxy group, ethoxymethoxy Group, methoxyethoxy group, ethoxyethoxy group, vinyloxy group, 1-propenyloxy group, 2-propenyloxy group, ethynyloxy group, 1-propynyloxy group, 2-propynyloxy group, aminooxy group, methylaminooxy group, Diethylaminooxy group, methoxycarbonylaminooxy group, phenoxy group, trichloromethoxy group, trifluoromethoxy group, difluoromethoxy group, 2,2,2-trifluoroethoxy group, pentafluoroethoxy group, 2-fluoroethoxy group, etc. It is done.
  • S (O) p R 3 include dimethylaminothio group, chloromethylthio group, 3-butenylthio group, ethynylthio group, 3-methylphenylthio group, methylsulfinyl group, ethylsulfinyl group, 1-butenylsulfinyl.
  • COR 3 examples include acetyl group, benzoyl group, propanoyl group, i-propylcarbonyl group, t-butylcarbonyl group, cyclopropylcarbonyl group, cyclobutylcarbonyl group, cyclopentylcarbonyl group, vinylcarbonyl group, 1-propenyl.
  • CO 2 R 3 examples include a methoxycarbonyl group, trifluoromethoxycarbonyl group, 1-pentenyloxycarbonyl group, 2-propynyloxycarbonyl group, phenoxycarbonyl group and the like.
  • Z in formula (7) is preferably a halogen atom, an unsubstituted or substituted amino group, an unsubstituted alkyl group, OR 3 , and SR 3 , and an unsubstituted or substituted group is More preferred are an amino group having, an unsubstituted alkyl group, OR 3 , and SR 3 .
  • the unsubstituted or substituted amino group in Z is preferably an unsubstituted amino group or a dialkylamino group, and the unsubstituted alkyl group preferably has 1 to 4 carbon atoms, and OR 3 Is preferably an alkoxy group having 1 to 4 carbon atoms, and SR 3 is preferably an alkylthio group having 1 to 4 carbon atoms.
  • m represents the number of substitutions of Z and is an integer from 0 to 3.
  • the plurality of Zs may be the same as or different from each other. It is particularly preferable that m is 0.
  • the halogenated picoline derivative represented by the formula (7) can be obtained, for example, by reacting a 2-substituted amino-6-methylpyridine derivative having a corresponding structure with a halogenating agent.
  • Step C1 the substance to be reacted with the halogenated picoline derivative represented by the formula (7) is a tetrazolylhydroxyimino derivative represented by the formula (8).
  • Y represents an unsubstituted or substituted alkyl group.
  • the unsubstituted or substituted alkyl group for Y include the same as those described above for R 1C .
  • the unsubstituted or substituted alkyl group is preferably an unsubstituted alkyl group, more preferably an unsubstituted alkyl group having 1 to 6 carbon atoms, and even more preferably a methyl group.
  • A is a halogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, a cyano group, an unsubstituted or substituted alkylsulfonyl group, or a nitro group Or an unsubstituted or substituted aryl group.
  • a halogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, and an unsubstituted or substituted aryl group in A are shown in the description of R 1C and Z above. The same thing as those.
  • the unsubstituted or substituted alkyl group is preferably an unsubstituted alkyl group or a haloalkyl group, and an unsubstituted alkyl group having 1 to 6 carbon atoms or having 1 to 6 carbon atoms.
  • a haloalkyl group is more preferred.
  • the unsubstituted or substituted alkoxy group is preferably an unsubstituted alkoxy group or a haloalkoxy group, and an unsubstituted alkoxy group having 1 to 6 carbon atoms or 1 to 6 carbon atoms. More preferred are 6 haloalkoxy groups.
  • Examples of the unsubstituted alkylsulfonyl group in A include a methylsulfonyl group, an ethylsulfonyl group, an n-propylsulfonyl group, an i-propylsulfonyl group, a t-butylsulfonyl group, and the like.
  • alkylsulfonyl group having a substituent examples include 2-pyridylmethylsulfonyl group, 3-pyridylmethylsulfonyl group, chloromethylsulfonyl group; cyanomethylsulfonyl group, 1-cyanoethylsulfonyl group, 2-cyanoethylsulfonyl group, nitromethylsulfonyl group Chloromethylsulfonyl group, fluoromethylsulfonyl group, difluoromethylsulfonyl group, trifluoromethylsulfonyl group, 2-fluoroethylsulfonyl group, 2,2,2-trifluoroethylsulfonyl group, methoxymethylsulfonyl group, ethoxymethylsulfonyl group 1-methoxyethylsulfonyl group, 2-methoxyethylsulfonyl group, 2-ch
  • the unsubstituted or substituted alkylsulfonyl group is preferably an unsubstituted alkylsulfonyl group, more preferably an unsubstituted alkylsulfonyl group having 1 to 6 carbon atoms.
  • n C represents the number of substitutions of A and is an integer of 0 to 5. When n C is 2 or more, A's may be the same or different from each other. n C is particularly preferably 0.
  • the reaction of the halogenated picoline derivative represented by formula (7) and the tetrazolylhydroxyimino derivative represented by formula (8) in Step C1 is a known reaction in which a halogeno group and a hydroxyl group are coupled.
  • the reaction can be performed according to the methods described in, for example, JP-A No. 2003-137875 and WO 03/016303 pamphlet. In general, the reaction is carried out in the presence of a base.
  • Examples of the base used in this reaction include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide; sodium carbonate, potassium carbonate, magnesium carbonate, Carbonates such as calcium carbonate; hydrides such as sodium hydride and calcium hydride; metal alkoxides such as sodium methoxide, sodium ethoxide and magnesium methoxide; triethylamine, diisopropylethylamine, pyridine, N, N-dimethylaminopyridine, 1,4-diazabicyclo [2.2.2] octane, 4- (dimethylamino) pyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.
  • alkali metal hydroxides such as sodium hydroxide and potassium hydroxide
  • alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide
  • organic bases such as non-5-ene; . These bases can be used alone or in combination of two or more.
  • the amount of the base used in Step C1 is usually 0.01 to 100 mol, preferably 0.1 to 5 mol, per 1 mol of the tetrazolylhydroxyimino derivative represented by the formula (8).
  • the reaction in Step C1 can be performed in the presence of a solvent or without a solvent.
  • the solvent to be used is not particularly limited as long as it is an inert solvent for this reaction.
  • hydrocarbon solvents such as pentane, hexane, heptane, benzene, toluene, xylene
  • halogen solvents such as dichloromethane, chloroform, carbon tetrachloride
  • nitrile solvents such as acetonitrile, propiononitrile
  • diethyl ether dioxane, tetrahydrofuran, etc.
  • Ether solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; water; and mixed solvents thereof; It is done.
  • the reaction of the halogenated picoline derivative represented by the formula (7) and the tetrazolylhydroxyimino derivative represented by the formula (8) is not particularly limited in the procedure and the like.
  • the reaction may be performed by adding a base and a tetrazolylhydroxyimino derivative represented by the formula (8) to an organic solvent solution containing the halogenated picoline derivative represented by the formula (7).
  • the temperature from the start to the end of the reaction in Step C1 may be kept constant or may be varied, but is usually in the range of ⁇ 70 ° C. to + 200 ° C., preferably ⁇ 20 ° C. to + 100 ° C. The temperature is in the range of ° C.
  • the reaction time is usually 30 minutes to 24 hours, although it depends on the reaction scale and the like.
  • the tetrazolyl oxime derivative represented by Formula (9) can be industrially advantageously obtained.
  • the tetrazolyl oxime derivative represented by the formula (9) is a novel substance, and is a useful substance as an intermediate for producing the tetrazolyl oxime derivative represented by the formula (10) described below.
  • R 1C , R 2C , Z, m, A, n C and Y have the same meaning as in formula (7) or formula (8).
  • Step C2 a tetrazolyloxime derivative represented by Formula (10) can be obtained by allowing a base to act on the reaction product in Step C1.
  • a base may be reacted with the reaction product, that is, the tetrazolyl oxime derivative represented by the formula (9) without purifying the reaction solution obtained through the step C1, or the step
  • the reaction product that is, the tetrazolyloxime derivative represented by the formula (9) can be isolated, and a base can be allowed to act thereon.
  • Examples of the purification operation include distillation, recrystallization or column chromatography.
  • the base used in Step C2 is not particularly limited as long as R 2C in the tetrazolyloxime derivative represented by Formula (9) can be eliminated.
  • Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide; sodium carbonate, potassium carbonate, magnesium carbonate, and calcium carbonate.
  • Carbonates such as sodium hydride and calcium hydride; metal alkoxides such as sodium methoxide, sodium ethoxide and magnesium methoxide; triethylamine, diisopropylethylamine, pyridine, N, N-dimethylaminopyridine, 1,4- Diazabicyclo [2.2.2] octane, 4- (dimethylamino) pyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] non- Organic bases such as 5-ene; and the like. These bases can be used alone or in combination of two or more.
  • the amount of the base used in Step C2 is usually 0.01 to 100 mol, preferably 0.1 to 5 mol, relative to 1 mol of the tetrazolyloxime derivative represented by the formula (9).
  • the amount of the base used in step C1 is taken into consideration.
  • the amount of base added in C2 can be adjusted.
  • the reaction in Step C2 can be performed in the presence of a solvent or without a solvent.
  • the solvent to be used is not particularly limited as long as it is an inert solvent for this reaction. As a specific example, the same thing as what was illustrated by description of process C1 can be mentioned. If the solvent used in step C2 is the same as the solvent used in step C1, there is no need to replace the solvent when moving from step C1 to step C2, which is advantageous in terms of manufacturing cost.
  • the reaction may be performed by adding a base to the reaction product in the step C1, that is, the organic solvent solution containing the tetrazolyloxime derivative represented by the formula (9).
  • the temperature from the start to the end of the reaction in Step C2 may be kept constant or may be varied, but is usually in the range of 0 ° C. to the boiling point of the solvent, preferably in the range of 10 to 60 ° C. Temperature.
  • the reaction time is usually 5 minutes to 24 hours, although it depends on the base concentration and reaction scale.
  • a normal post-treatment operation can be performed. And the tetrazolyl oxime derivative represented by the target formula (10) can be isolated.
  • known and conventional purification means such as distillation, extraction, recrystallization or column chromatography can be employed.
  • the structure of the target product can be identified and confirmed by measuring 1 H-NMR spectrum, IR spectrum, mass spectrum, elemental analysis or the like.
  • the tetrazolyl oxime derivative represented by the formula (10) obtained by the production method of the present invention can be converted into a salt.
  • the salt can be produced by reacting an acid with the tetrazolyloxime derivative represented by the formula (10) according to a conventional method.
  • the tetrazolyl oxime derivative represented by the formula (10) obtained by the production method of the present invention or a salt thereof is suitable as an active ingredient such as a bactericide.
  • the fungicide can be used, for example, as an agrochemical formulation that helps the growth of agricultural and horticultural crops, as an anti-fouling agent for shellfish and shellfish, or as an antibacterial or antifungal agent for walls, bathtubs, shoes, or clothes.
  • a reactor purged with nitrogen was charged with 40 ml of N, N-dimethylformamide, and 5.23 g of sodium hydride (purity 55%) and 160 ml of toluene were added thereto.
  • a solution of 20.8 g of (6-methyl-pyridin-2-yl) -carbamic acid t-butyl ester in 50 ml of toluene was added dropwise at a temperature range of 20 ° C. to 25 ° C. over 20 minutes. After completion of the dropwise addition, the mixture was stirred for 30 minutes in the temperature range of 20 ° C to 25 ° C. Thereafter, the mixture was cooled to 5 ° C.
  • Example B2 Production of benzoyl- (6-bromomethyl-pyridin-2-yl) -carbamic acid t-butyl ester
  • Example B3 Production of benzoyl- ⁇ 6-[[Z]-(1-methyl-1H-5-tetrazolyl) phenylmethyleneaminooxymethyl) -2-pyridyl ⁇ carbamic acid t-butyl ester
  • Example B2 To the reaction solution obtained in Example B2, 37.2 g of 20% sodium hydroxide was added, and the mixture was stirred at a temperature range of 20 ° C. to 25 ° C. for 30 minutes. Thereafter, 18.9 g of (1-methyl-1H-5-tetrazolyl) -phenyl-methanone oxime was added and stirred at a temperature range of 20 ° C. to 25 ° C. for 3.5 hours. It was confirmed by thin layer chromatography that the target product disappeared and the compound represented by the formula (f) was produced. The reaction solution was not post-treated and used as such in Example B4.
  • Example B4 Preparation of ⁇ 6-([Z]-(1-methyl-1H-5-tetrazolyl) phenylmethyleneaminooxymethyl) -2-pyridyl ⁇ carbamic acid t-butyl ester
  • Example B3 To the reaction solution obtained in Example B3, 37.2 g of 20% sodium hydroxide was added and stirred at 40 ° C. for 15 hours. It was confirmed by thin layer chromatography that the raw material disappeared and the target product was produced. Thereafter, the reaction solution was separated into an organic layer and an aqueous layer. The organic layer was washed with 93 ml of 1N sodium hydroxide. The aqueous layer was extracted with 23 ml of chlorobenzene, combined with the previous organic layer, and washed with 47 ml of saturated brine. The solvent was removed under reduced pressure, methanol was added to the residue, and the mixture was concentrated under reduced pressure. Methanol addition-vacuum concentration was further performed twice.
  • Example B5 Production of acetyl- (6-methyl-pyridin-2-yl) -carbamic acid t-butyl ester
  • a compound represented by the formula (h) was produced in the same manner as in Production Example B1, except that acetyl chloride was used instead of benzoyl chloride.
  • the melting point of the compound was 77.4-77.5 ° C.
  • Example B6 Production of acetyl- (6-bromomethyl-pyridin-2-yl) -carbamic acid t-butyl ester
  • Example B7 Preparation of ⁇ 6-([Z]-(1-methyl-1H-5-tetrazolyl) phenylmethylene-aminooxymethyl) -2-pyridyl ⁇ carbamic acid t-butyl ester
  • the reaction solution was poured into a mixed solution of 500 ml each of a saturated aqueous solution of ammonium chloride, a saturated aqueous solution of sodium bicarbonate and a saturated aqueous solution of sodium chloride, and then extracted with ethyl acetate. The extract was dried over anhydrous magnesium sulfate, filtered and concentrated. Thereafter, the column was purified to obtain 81 g (74.7%) of the desired product.
  • the obtained residue was cooled to 10 ° C. or lower, 46.03 g (43 ml) of diisopropylethylamine and 43.08 g (58 ml) of diethyl phosphite were added, and the mixture was aged for 16.5 hours at room temperature. After confirming the disappearance of the raw material by thin layer chromatography, it was washed with 300 ml of 3N hydrochloric acid and further with 500 ml of saturated saline. It was dried over anhydrous magnesium sulfate and filtered to obtain a 2-bis (t-butoxycarbonyl) amino-6-bromomethyl-pyridine solution.
  • Example B10 Preparation of ⁇ 6-([Z]-(1-methyl-1H-5-tetrazolyl) phenylmethylene-aminooxymethyl) -2-pyridyl ⁇ carbamic acid t-butyl ester
  • the temperature of the reaction solution was raised to 40 ° C., and 4.29 g (30 mmol) of a 28 wt% NaOH aqueous solution was charged.
  • the mixture was stirred at 40 ° C. for 2.5 hours. Then, it left still overnight. Subsequently, it stirred at 40 degreeC for 3.5 hours.
  • the organic phase obtained by separating the reaction solution was washed successively with an aqueous NaOH solution having a concentration of 1 mol / L and water.
  • the organic phase after washing was concentrated with an evaporator, and the resulting residue was crystallized with methanol to obtain 6.08 g (14.8 mmol, yield 99%) of white crystals.
  • the white crystals obtained showed the same physical properties as compound number (3) -8 in Table 3 of WO 03/016303.
  • the obtained white crystals were confirmed to be a compound represented by the formula (q).
  • Example C3 A compound represented by the formula (r) was obtained in the same manner as in Example C2, except that the compound represented by the formula (n) was replaced with 2- (t-butoxycarbonylmethoxycarbonylamino) -6-bromomethylpyridine. .
  • the NMR measurement results of the compound represented by the formula (r) were as follows. 1 H-NMR (CDCl 3 , ⁇ ppm): 1.41 (s, 9H), 3.77 (s, 3H), 3.79 (s, 3H), 5.38 (s, 2H), 7.18 (d, 1H), 7.26 (d, 1H), 7.37 (m, 2H), 7.45 (m, 1H), 7.51 (m, 1H), 7.78 (t, 1H).
  • the pyridine ring-containing compound according to the present invention is useful as an intermediate for producing a tetrazolyl oxime derivative that can be synthesized industrially advantageously and exhibits bactericidal activity. Further, according to the production method of the present invention, a 2-substituted amino-6-halomethylpyridine derivative can be obtained with high selectivity and high yield, and a tetrazolyloxime derivative excellent in controlling effect against plant diseases can be obtained. It can be produced industrially advantageously.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pyridine Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
PCT/JP2011/055809 2010-03-12 2011-03-11 ピリジン環含有化合物、及びハロゲン化ピコリン誘導体及びテトラゾリルオキシム誘導体の製造方法 WO2011111831A1 (ja)

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BR122017023123-5A BR122017023123B1 (pt) 2010-03-12 2011-03-11 Método para produzir derivado de picolina halogenada
JP2012504543A JP5627038B2 (ja) 2010-03-12 2011-03-11 ピリジン環含有化合物
CN201180012762.8A CN102791691B (zh) 2010-03-12 2011-03-11 含有吡啶环的化合物、及卤代甲基吡啶衍生物以及四唑基肟衍生物的制造方法
BR112012022823-4A BR112012022823B1 (pt) 2010-03-12 2011-03-11 Composto contendo anel de piridina
RU2012138410/04A RU2512344C1 (ru) 2010-03-12 2011-03-11 Соединение, содержащие кольцо пиридина, и способ получения галогенированного производного пиколина и производного тетразолилоксима
BR122017023130-8A BR122017023130B1 (pt) 2010-03-12 2011-03-11 Derivado de tetrazoliloxima, métodos de produção de derivados de tetrazoliloxima
BR122017023128-6A BR122017023128B1 (pt) 2010-03-12 2011-03-11 Método para produzir derivado de picolina brominada
AU2011225122A AU2011225122B8 (en) 2010-03-12 2011-03-11 Compound containing pyridine ring and method for producing halogenated picoline derivative and tetrazolyloxime derivative
KR1020127023288A KR101409137B1 (ko) 2010-03-12 2011-03-11 피리딘 고리 함유 화합물, 및 할로겐화피콜린 유도체 및 테트라졸릴옥심 유도체의 제조 방법
US13/583,733 US8841458B2 (en) 2010-03-12 2011-03-11 Compound containing pyridine ring and method for producing halogenated picoline derivative and tetrazolyloxime derivative
EP11753489.1A EP2546236A4 (de) 2010-03-12 2011-03-11 Verbundstoff mit einem pyridinring sowie verfahren zur herstellung eines halogenierten picolinderivats und eines tetrazolyloximderivats
IL221847A IL221847A (en) 2010-03-12 2012-09-09 A compound containing a pyridine ring and a method for producing a picolin derivative
IL229968A IL229968A (en) 2010-03-12 2013-12-17 Tetrazolyl Oxide Derivatives
IL229967A IL229967A (en) 2010-03-12 2013-12-17 Production method for a picoline-derived derivative and a production method for a tetrazolyl-oxy derivative
US14/173,338 US8962848B2 (en) 2010-03-12 2014-02-05 Compound containing pyridine ring and method for producing halogenated picoline derivative and tetrazolyloxime derivative
US14/173,330 US9012653B2 (en) 2010-03-12 2014-02-05 Compound containing pyridine ring and method for producing halogenated picoline derivative and tetrazolyloxime derivative
US14/173,323 US9018385B2 (en) 2010-03-12 2014-02-05 Compound containing pyridine ring and method for producing halogenated picoline derivative and tetrazolyloxime derivative
US14/173,352 US9000178B2 (en) 2010-03-12 2014-02-05 Compound containing pyridine ring and method for producing halogenated picoline derivative and tetrazolyloxime derivative

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US14/173,338 Division US8962848B2 (en) 2010-03-12 2014-02-05 Compound containing pyridine ring and method for producing halogenated picoline derivative and tetrazolyloxime derivative
US14/173,330 Division US9012653B2 (en) 2010-03-12 2014-02-05 Compound containing pyridine ring and method for producing halogenated picoline derivative and tetrazolyloxime derivative
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